CN109772322A - A kind of coal gas layer dehydrogenation catalyst and preparation method thereof - Google Patents
A kind of coal gas layer dehydrogenation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN109772322A CN109772322A CN201711119007.5A CN201711119007A CN109772322A CN 109772322 A CN109772322 A CN 109772322A CN 201711119007 A CN201711119007 A CN 201711119007A CN 109772322 A CN109772322 A CN 109772322A
- Authority
- CN
- China
- Prior art keywords
- zirconium sulfate
- copper
- catalyst
- supported copper
- aluminium oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003034 coal gas Substances 0.000 title description 5
- 238000006356 dehydrogenation reaction Methods 0.000 title description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 78
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052802 copper Inorganic materials 0.000 claims abstract description 45
- 239000010949 copper Substances 0.000 claims abstract description 45
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims abstract description 43
- 239000003245 coal Substances 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 16
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 13
- 239000007921 spray Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 31
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 2
- 235000019253 formic acid Nutrition 0.000 claims 2
- 230000031709 bromination Effects 0.000 claims 1
- 238000005893 bromination reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 230000008901 benefit Effects 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 26
- 239000000523 sample Substances 0.000 description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 239000000571 coke Substances 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000007084 catalytic combustion reaction Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910025794 LaB6 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- ZSDJVGXBJDDOCD-UHFFFAOYSA-N benzene dioctyl benzene-1,2-dicarboxylate Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1=CC=CC=C1 ZSDJVGXBJDDOCD-UHFFFAOYSA-N 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The present invention discloses a kind of coal bed gas deoxidation catalyst, the catalyst contains the aluminium oxide and zirconium sulfate of supported copper, the aluminium oxide of the supported copper is wrapped in around zirconium sulfate, the aluminium oxide of the supported copper and the weight ratio of zirconium sulfate are 8:1-2:1, on the basis of the alumina weight of supported copper, content of the copper in terms of oxide is 5wt%-25wt%；Copper-containing compound and aluminum hydroxide slurry: being uniformly mixed by the preparation method of the catalyst, including following content first, then sprays mixed liquor around zirconium sulfate, and coal bed gas deoxidation catalyst is made after drying, roasting.The advantages that catalyst is active high, reaction temperature is low, preparation method is simple, at low cost for coal bed gas deoxidation.
Description
Technical field
The present invention relates to a kind of coal gas layer dehydrogenation catalysts and preparation method thereof, relate in particular to a kind of low temperature high activity
Coal gas layer dehydrogenation catalyst and preparation method thereof.
Background technique
China is coal production big country, every year because coal production will a large amount of various concentrations of output coal bed gas, exploitation
Effective gas utilization technology, the direct emission for reducing methane are that China builds energy saving and environment friendly mode of sustainable development, beats
Make a component part of low-carbon economy system.In conjunction with energy-saving and emission-reduction and to the raising of environmental requirement, conscientiously reasonable exploitation
This low-grade energy of coal bed gas, and it is translated into available resource well, expand use scope and the rule of coal bed gas
Mould improves the utilization efficiency of coal bed gas, has the double meaning of energy conservation and environmental protection, meets planning of the country to energy policy, symbol
Control of the International Environmental Protection tissue to greenhouse effects is closed, more meets China and develops the support energetically used to low-grade energy, promote
Fast development of the country to coal gas industry.
The key that cbm development utilizes is to remove oxygen therein, and existing coal bed gas deoxidation technology mainly has transformation
Adsorption separation method, coke combustion method, catalytic deoxidation method etc..Chinese patent ZL85103557 discloses a kind of using pressure-variable adsorption
The method of method separation and concentration methane from coal bed gas.Under normal circumstances, the oxygen that methane discharges exhaust gas in concentration purification process contains
Amount is also concentrated raising, due to inevitably containing 5 ~ 15% methane in exhaust gas, the exhaust gas of discharge is caused to be in the quick-fried of methane
Fried limit range, there are explosion dangers, this is restricted the application of the technology.
Coke combustion method deoxidation (ZL02113627.0,200610021720.1) is under the high temperature conditions, to be rich in methane gas
Oxygen and coke gasification reaction in body, while portion of methane reacts to reach deoxidation purpose with oxygen.The advantage is that about 70% oxygen with
Coke gasification reaction, 30% oxygen and methane reaction, therefore methane losses are smaller.But disadvantage is to consume valuable coke resource, burnt
Charcoal consuming cost accounts for about 50% or so of whole service expense.In addition, coke deoxidization method large labor intensity, ring when adding coke, slagging tap
Border dust is big, it is difficult to automatic operation and large-scale production is realized, and with variform sulfide in coke, after leading to deoxygenation
Sulfur content increases in gas.
The essence of catalytic deoxidation process is the catalysis burning of methane under fuel-rich oxygen-lean atmosphere, under appropriate catalyst action,
By CH4Oxidation is converted into CO2And H2Oxygen content in coal bed gas can be dropped to 0.5% hereinafter, and completely eliminating operation by O, this process
The security risk of process.Technological operation simultaneously is easy, and convenient for automatically controlling and expanding on a large scale, equipment is simple, from economy angle
For degree, which also has preferable commercial value.Catalytic deoxidation can be divided into precious metal catalyst according to catalyst activity component
Agent and non-precious metal catalyst two major classes.
The technology of research loaded noble metal catalyst is more mature both at home and abroad.The catalyst as where Chinese Academy of Sciences's Dalian materialization
Addition has the cerium component of storage oxygen function in system, prepares novel supported palladium noble metal catalyst, can be by first
Alkane concentration is 39.15%, and after the coal bed gas deoxidation processing that oxygen concentration is 12.6%, oxygen concentration is within 0.1% in production gas, oxygen
Gas high conversion rate is in 96%.Since noble metal catalyst is expensive and resource is limited, application range is restricted.Rather than your gold
It is cheap and easy to get to belong to oxide catalyst raw material, thus receives great attention.But base metal receptor 1 activity is limited, and is needed higher
Temperature reacted, energy consumption is larger.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of coal bed gas deoxidation catalyst and preparation method thereof.The catalysis
The advantages that agent is active high, reaction temperature is low, preparation method is simple, at low cost.
A kind of coal bed gas deoxidation catalyst, the catalyst contain the aluminium oxide and zirconium sulfate of supported copper, the supported copper
Aluminium oxide be wrapped in around zirconium sulfate, the weight ratio of the aluminium oxide of the supported copper and zirconium sulfate is 8:1-2:1, preferably
6:1-3:1, on the basis of the alumina weight of supported copper, content of the copper in terms of oxide is 5wt%-25wt%, preferably 10 wt%-
20wt%。
In above-mentioned catalyst, the aluminium oxide of the supported copper being wrapped in around zirconium sulfate with a thickness of 15 μm -130 μm,
Preferably 20 μm -100 μm.
In above-mentioned catalyst, the zirconium sulfate can be spherical or bar shaped, preferably spherical；Zirconium sulfate equivalent diameter is 1mm-
8mm, preferably 3mm-5mm.
A kind of preparation method of coal bed gas deoxidation catalyst, including following content: first by copper-containing compound and hydroxide
Aluminium paste liquid is uniformly mixed, and then sprays mixed liquor around zirconium sulfate, and coal bed gas deoxidation catalysis is made after drying, roasting
Agent.
In the above method, the zirconium sulfate is prepared using commercial goods or according to the prior art.The hydrogen
Aluminium oxide slurries generally use pseudoboehmite slurry.Boehmite also known as monohydrate alumina or false boehmite, point
Minor is AlOOHnH2O(n=0.08-0.62).For the preparation method of aluminum hydroxide slurry, there is no particular limitation, can be with
It for various methods commonly used in the art, such as can be aluminium alcoholates Hydrolyze method, the acid system of aluminium salt or aluminate or alkaline process, NaA1O2It is molten
Liquid is passed through CO2Carbonizatin method etc..Specific operating method is known to those skilled in the art, and details are not described herein.
In the above method, the copper-containing compound can for one of copper nitrate, copper sulphate, copper bromide, copper chloride or
It is several.
In the above method, the drying time is 1-5h, and preferably 2-4h, drying temperature is 90-150 DEG C, preferably 100-130
℃；The calcining time is 3-8h, and preferably 4-6h, temperature is 300-700 DEG C, preferably 400-500 DEG C.
In the above method, contain 2,5- dihydroxy-terephthalic acid (TPA) or 1 in the mixed liquor, in 3,5- benzenetricarboxylic acids
At least one, 2,5- dihydroxy-terephthalic acid (TPA) or 1, quality of at least one of 3, the 5- benzenetricarboxylic acids in mixed liquor
Content is 0.5%-10%, preferably 2%-7%.2,5- dihydroxy-the terephthalic acid (TPA) or 1,3,5- benzenetricarboxylic acid being added in mixed liquor
There is stronger coordination effect with copper ion, can be improved the dispersion degree of copper on alumina, further increase the work of catalyst
Property.
In the above method, zirconium sulfate preferably uses vapor volume content for 0.5%-5% before spraying mixed liquor, into one
The vapor nitrogen mixture for walking preferred 1%-4% handles it, treatment temperature be 100-200 DEG C, preferably 120-180 DEG C,
The processing time is 1-15 min, further preferred 3-10 min.Zirconium sulfate table can be improved using the zirconium sulfate of steam treatment
The hydrophily in face is conducive to spraying for mixed liquor, improves the aluminium oxide of supported copper with the interaction force between zirconium sulfate, avoids
The aluminium oxide of supported copper falls off around zirconium sulfate, improves the stability of catalyst.
Result of study shows that the mechanism of coal bed gas catalysis burning is surface dissociation of the methane in catalyst for catalytic combustion first
For CHxThen species, x < 4 carry out oxidation reaction with absorption oxygen or Lattice Oxygen.The application is by catalyst for catalytic combustion in sulfuric acid
Around zirconium, zirconium sulfate has the function of stronger Methane Activation, the methane after activation compared to catalyst for catalytic combustion at low temperature
Substance, which is diffused into catalyst for catalytic combustion coating, to be reacted, it is easier to quickly be burnt, be significantly improved catalyst
Activity.
Specific embodiment
A kind of work of coal bed gas deoxidation catalyst of the present invention and preparation method thereof is further illustrated below with reference to embodiment
With and effect, but following embodiment is not construed as limiting the invention.% is volumetric concentration unless otherwise specified in the application.
Catalyst of the invention can using transmission electron microscope observing, electron diffraction analysis and Elemental Composition analyse etc. means come
Confirm its package structure, and measures composition.The determination of catalyst package structure is specifically with the following method: using Japan JEOL
2100 LaB6 high-resolution-ration transmission electric-lens of company JEM, 0.23 nm of resolution ratio, the X ray energy dispersion spectroscopy equipped with EDAX company
Instrument (EDX), sample is placed in agate mortar and is fully ground, and then ultrasonic wave disperses 20 min in dehydrated alcohol.Take 2-3 drop
Suspended drop on the micro-grid carbon film that copper mesh supports, after sample drying to sample carry out TEM observation, electron diffraction analysis and
Elemental Composition analysis.
Embodiment 1
Prepare aluminum hydroxide slurry using aluminium isopropoxide Hydrolyze method: by water, 120:1 is mixed in molar ratio with aluminium isopropoxide, hydrolysis temperature
Degree control is at 80 DEG C -85 DEG C, after so that aluminium isopropoxide is hydrolyzed 1.5h, carries out aging, aging temperature control is at 90 DEG C -95 DEG C, aging
Time is 18h, obtains the aluminum hydroxide slurry that solid content is 21.3wt%.
It sprays process: being first uniformly mixed copper nitrate and aluminum hydroxide slurry, then spray 500g zirconium sulfate (city with mixed liquor
Product is sold, equivalent diameter is 4 mm), coal bed gas deoxidation catalyst is made after drying, roasting, the drying time is 4h, is done
Dry temperature is 100 DEG C；The calcining time 6h, temperature are 400 DEG C.
Catalyst property is as follows: the aluminium oxide of supported copper is wrapped in around zirconium sulfate, the aluminium oxide of the supported copper with
The weight ratio of zirconium sulfate is 4:1, and on the basis of the alumina weight of supported copper, content of the copper in terms of oxide is 15wt%.It is described
The aluminium oxide of the supported copper around zirconium sulfate is wrapped in a thickness of 60 μm.
Catalyst performance, unstripped gas composition are as follows: CH are evaluated by probe reaction of coal bed gas deoxidation420 vol%, O2 3
Vol%, surplus N2.Reaction temperature is 450 DEG C, and volume space velocity is 10000 h-1, after stable reaction, on-line chromatograph detection is anti-
O in the tail gas for answering device to export2Concentration is 0.56%, O in the tail gas of 100 h post-reactors of operating outlet2Concentration is 0.7%.
Embodiment 2
Prepare aluminum hydroxide slurry using aluminium isopropoxide Hydrolyze method: by water, 120:1 is mixed in molar ratio with aluminium isopropoxide, hydrolysis temperature
Degree control is at 80 DEG C -85 DEG C, after so that aluminium isopropoxide is hydrolyzed 1.5h, carries out aging, aging temperature control is at 90 DEG C -95 DEG C, aging
Time is 18h, obtains the aluminum hydroxide slurry that solid content is 21.3wt%.
It sprays process: being first uniformly mixed copper nitrate and aluminum hydroxide slurry, then spray 500g sulfuric acid with mixed liquor
Coal bed gas deoxidation catalyst is made in zirconium (commercial product, equivalent diameter be 5 mm) after drying, roasting, and the drying time is
4h, drying temperature are 100 DEG C；The calcining time 6h, temperature are 400 DEG C.
Catalyst property is as follows: the aluminium oxide of supported copper is wrapped in around zirconium sulfate, the aluminium oxide of the supported copper with
The weight ratio of zirconium sulfate is 3:1, and on the basis of the alumina weight of supported copper, content of the copper in terms of oxide is 20wt%.
Catalyst performance, unstripped gas composition are as follows: CH are evaluated by probe reaction of coal bed gas deoxidation420 vol%, O2 3
Vol%, surplus N2.Reaction temperature is 450 DEG C, and volume space velocity is 10000 h-1, after stable reaction, on-line chromatograph detection is anti-
O in the tail gas for answering device to export2Concentration is 0.48%.
Embodiment 3
Using the preparing aluminum hydroxide through carbonization slurries for being passed through carbon dioxide gas into sodium aluminate solution: 30wt%CO will be contained2
CO2/N2Gaseous mixture is passed through in sodium aluminate solution, and plastic reaction is carried out at 30 DEG C, and control reaction end pH is 10.5-
11.0, after the reaction was completed, aging, washing through deionized water to filtrate pH at 60 DEG C is 6.5, and obtaining solid content is 31.2wt%
Aluminum hydroxide slurry.
It sprays process: being first uniformly mixed copper nitrate and aluminum hydroxide slurry, then spray 500g sulfuric acid with mixed liquor
Coal bed gas deoxidation catalyst is made in zirconium (commercial product, equivalent diameter be 3 mm) after drying, roasting, and the drying time is
4h, drying temperature are 100 DEG C；The calcining time 6h, temperature are 400 DEG C.
Catalyst property is as follows: the aluminium oxide of supported copper is wrapped in around zirconium sulfate, the aluminium oxide of the supported copper with
The weight ratio of zirconium sulfate is 6:1, and on the basis of the alumina weight of supported copper, content of the copper in terms of oxide is 10wt%.
Catalyst performance, unstripped gas composition are as follows: CH are evaluated by probe reaction of coal bed gas deoxidation420 vol%, O2 3
Vol%, surplus N2.Reaction temperature is 450 DEG C, and volume space velocity is 10000 h-1, after stable reaction, on-line chromatograph detection is anti-
O in the tail gas for answering device to export2Concentration is 0.59%.
Embodiment 4
With the different place of embodiment 1 be in the mixed liquor containing mass content be 6% 2,5- dihydroxy-to benzene
Dioctyl phthalate.
Catalyst performance, unstripped gas composition are as follows: CH are evaluated by probe reaction of coal bed gas deoxidation420 vol%, O2 3
Vol%, surplus N2.Reaction temperature is 450 DEG C, and volume space velocity is 10000 h-1, after stable reaction, on-line chromatograph detection is anti-
O in the tail gas for answering device to export2Concentration is 0.
Embodiment 5
It is the 1,3,5- benzenetricarboxylic acid for being 3% containing mass content in the mixed liquor with the different place of embodiment 1.
Catalyst performance, unstripped gas composition are as follows: CH are evaluated by probe reaction of coal bed gas deoxidation420 vol%, O2 3
Vol%, surplus N2.Reaction temperature is 450 DEG C, and volume space velocity is 10000 h-1, after stable reaction, on-line chromatograph detection is anti-
O in the tail gas for answering device to export2Concentration is 0.
Embodiment 6
With the different place of embodiment 1 be zirconium sulfate used before spraying mixed liquor vapor volume content for 1% water
Steam nitrogen mixture handles it, and treatment temperature is 180 DEG C, and the processing time is 3min.
Catalyst performance, unstripped gas composition are as follows: CH are evaluated by probe reaction of coal bed gas deoxidation420 vol%, O2 3
Vol%, surplus N2.Reaction temperature is 450 DEG C, and volume space velocity is 10000 h-1, after stable reaction, on-line chromatograph detection is anti-
O in the tail gas for answering device to export2Concentration is 0.53%, O in the tail gas of 100 h post-reactors of operating outlet2Concentration is 0.57%.
Embodiment 7
With the different place of embodiment 1 be zirconium sulfate used before spraying mixed liquor vapor volume content for 4% water
Steam nitrogen mixture handles it, and treatment temperature is 120 DEG C, and the processing time is 1010 min of 1-15.
Catalyst performance, unstripped gas composition are as follows: CH are evaluated by probe reaction of coal bed gas deoxidation420 vol%, O2 3
Vol%, surplus N2.Reaction temperature is 450 DEG C, and volume space velocity is 10000 h-1, after stable reaction, on-line chromatograph detection is anti-
O in the tail gas for answering device to export2Concentration is 0.49%, O in the tail gas of 100 h post-reactors of operating outlet2Concentration is 0.51%.
Claims (13)
1. a kind of coal bed gas deoxidation catalyst, it is characterised in that: the catalyst contains the aluminium oxide and zirconium sulfate of supported copper, institute
The aluminium oxide for stating supported copper is wrapped in around zirconium sulfate, and the aluminium oxide of the supported copper and the weight ratio of zirconium sulfate are 8:1-2:
1, on the basis of the alumina weight of supported copper, content of the copper in terms of oxide is 5wt%-25wt%.
2. catalyst according to claim 1, it is characterised in that: the catalyst contains the aluminium oxide and sulfuric acid of supported copper
The aluminium oxide of zirconium, the supported copper is wrapped in around zirconium sulfate, and the aluminium oxide of the supported copper and the weight ratio of zirconium sulfate are
6:1-3:1, on the basis of the alumina weight of supported copper, content of the copper in terms of oxide is 10 wt%-20wt%.
3. catalyst according to claim 1, it is characterised in that: the oxygen of the supported copper being wrapped in around zirconium sulfate
Change aluminium with a thickness of 15 μm -130 μm, the zirconium sulfate is spherical or bar shaped, and zirconium sulfate equivalent diameter is 1mm-8mm.
4. catalyst according to claim 3, it is characterised in that: the oxygen of the supported copper being wrapped in around zirconium sulfate
Change aluminium with a thickness of 20 μm -100 μm, the zirconium sulfate is spherical shape, and zirconium sulfate equivalent diameter is 3mm-5mm.
5. the preparation method of any catalyst of Claims 1-4, it is characterised in that: including following content: first by cupric
Compound and aluminum hydroxide slurry are uniformly mixed, and then spray mixed liquor around zirconium sulfate, are made after drying, roasting
Coal bed gas deoxidation catalyst.
6. according to the method described in claim 5, it is characterized by: the zirconium sulfate is using commercial goods or according to existing skill
It is prepared by art；The aluminum hydroxide slurry uses pseudoboehmite slurry.
7. according to the method described in claim 5, it is characterized by: the copper-containing compound is copper nitrate, copper sulphate, bromination
One or more of copper, copper chloride.
8. according to the method described in claim 5, it is characterized by: the drying time is 1-5h, drying temperature 90-150
℃；The calcining time is 3-8h, and temperature is 300-700 DEG C.
9. according to the method described in claim 8, it is characterized by: the drying time is 2-4h, drying temperature 100-130
℃；The calcining time is 4-6h, and temperature is 400-500 DEG C.
10. according to the method described in claim 5, it is characterized by: containing 2,5- dihydroxy-in the mixed liquor to benzene two
Formic acid or 1, at least one of 3,5- benzenetricarboxylic acids, 2,5- dihydroxy-terephthalic acid (TPA) or 1, in 3,5- benzenetricarboxylic acids extremely
A kind of few mass content in mixed liquor is 0.5%-10%.
11. according to the method described in claim 10, it is characterized by: 2,5- dihydroxy-terephthalic acid (TPA) or 1,3,5- benzene three
Mass content of at least one of the formic acid in mixed liquor is 2%-7%.
12. according to the method described in claim 5, it is characterized by: zirconium sulfate uses vapor body before spraying mixed liquor
Product content be 0.5%-5% vapor nitrogen mixture it is handled, treatment temperature be 100-200 DEG C, processing the time be
1-15 min。
13. according to the method for claim 12, it is characterised in that: zirconium sulfate uses vapor body before spraying mixed liquor
The vapor nitrogen mixture that product content is 1%-4% handles it, and treatment temperature is 120-180 DEG C, and the processing time is 3-
10 min。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711119007.5A CN109772322B (en) | 2017-11-14 | 2017-11-14 | Coal bed gas deoxidation catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711119007.5A CN109772322B (en) | 2017-11-14 | 2017-11-14 | Coal bed gas deoxidation catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109772322A true CN109772322A (en) | 2019-05-21 |
| CN109772322B CN109772322B (en) | 2021-08-31 |
Family
ID=66494815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711119007.5A Active CN109772322B (en) | 2017-11-14 | 2017-11-14 | Coal bed gas deoxidation catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109772322B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005246197A (en) * | 2004-03-03 | 2005-09-15 | Idemitsu Kosan Co Ltd | Method for manufacturing molding of inorganic oxide |
| CN101322942A (en) * | 2008-07-29 | 2008-12-17 | 西南化工研究设计院 | Oxygen-containing coal bed gas deoxidation catalyst and preparation thereof as well as applications |
| CN102433182A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Catalytic deoxidation method for coalbed gas in coal mine area |
| CN104888792A (en) * | 2015-06-23 | 2015-09-09 | 北京联合大学 | Low-temperature methane catalytic combustion catalyst preparation method |
| CN108067230A (en) * | 2016-11-11 | 2018-05-25 | 中国石油化工股份有限公司抚顺石油化工研究院 | A kind of preparation method of non-precious metal catalyst |
-
2017
- 2017-11-14 CN CN201711119007.5A patent/CN109772322B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005246197A (en) * | 2004-03-03 | 2005-09-15 | Idemitsu Kosan Co Ltd | Method for manufacturing molding of inorganic oxide |
| CN101322942A (en) * | 2008-07-29 | 2008-12-17 | 西南化工研究设计院 | Oxygen-containing coal bed gas deoxidation catalyst and preparation thereof as well as applications |
| CN102433182A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Catalytic deoxidation method for coalbed gas in coal mine area |
| CN104888792A (en) * | 2015-06-23 | 2015-09-09 | 北京联合大学 | Low-temperature methane catalytic combustion catalyst preparation method |
| CN108067230A (en) * | 2016-11-11 | 2018-05-25 | 中国石油化工股份有限公司抚顺石油化工研究院 | A kind of preparation method of non-precious metal catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109772322B (en) | 2021-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101920201B (en) | Method for preparing cobalt-based Fischer-Tropsch synthesis catalyst | |
| CN101947457A (en) | Ventilation air methane combustion catalyst and preparation method thereof | |
| CN110624557B (en) | Co-based catalyst for photo-thermal coupling catalysis of CO methanation | |
| CN103933978A (en) | Supported nanocatalyst for catalytic conversion of carbon dioxide as well as preparation method and application thereof | |
| CN110813320A (en) | Carbon-supported palladium-based alloy catalyst, preparation method thereof and application of catalyst in preparation of styrene | |
| CN101912783B (en) | Catalyst for combustion of ventilation air methane and preparation method thereof | |
| CN113908840A (en) | Fe-based multifunctional catalyst and preparation method and application thereof | |
| CN109225219A (en) | Copper with schottky junction structure-porous silica titanium composite material preparation method and application | |
| CN109772324A (en) | A kind of preparation method of O composite metallic oxide catalyst | |
| CN108514881A (en) | One kind being used for NH3Cu-Ce catalyst, preparation method and the application of the nano bar-shape structure of catalysis oxidation | |
| CN109772441A (en) | A kind of catalyst of core-shell structure and its preparation method and application | |
| CN105363457B (en) | For carboxylic ester hydrogenation catalyst | |
| CN104084232A (en) | Preparation method for catalyst used for deoxidation of biological fatty alcohol | |
| CN109772322A (en) | A kind of coal gas layer dehydrogenation catalyst and preparation method thereof | |
| CN108067230A (en) | A kind of preparation method of non-precious metal catalyst | |
| CN105363454B (en) | Hydrogenation catalyst | |
| CN105642289A (en) | Preparation method of catalyst for complete methanation of syngas | |
| CN103769102B (en) | A kind of cobalt-base catalyst and its preparation method and application | |
| CN102441388B (en) | Preparation method for cobalt-base Fischer Tropsch synthetic catalyst with high stability | |
| CN102441387B (en) | Method for preparing high-activity cobalt-based Fischer-Tropsch synthetic catalyst | |
| CN103769227A (en) | Modified silica gel carrier, and preparation method and applications thereof | |
| CN109126791A (en) | A kind of Cu (II)-mTiO2Loaded photocatalyst and its preparation and application | |
| CN109772440A (en) | A kind of coal gas layer catalyst for catalytic combustion and preparation method thereof | |
| CN105435797B (en) | Carboxylic ester hydrogenation catalyst | |
| CN111889114B (en) | Catalyst with shell-core structure and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231008 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |